DE4033157C2 - - Google Patents
Info
- Publication number
- DE4033157C2 DE4033157C2 DE19904033157 DE4033157A DE4033157C2 DE 4033157 C2 DE4033157 C2 DE 4033157C2 DE 19904033157 DE19904033157 DE 19904033157 DE 4033157 A DE4033157 A DE 4033157A DE 4033157 C2 DE4033157 C2 DE 4033157C2
- Authority
- DE
- Germany
- Prior art keywords
- disilanes
- distillation residues
- weight
- added
- hydrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 238000004821 distillation Methods 0.000 claims description 29
- 230000007062 hydrolysis Effects 0.000 claims description 24
- 238000006460 hydrolysis reaction Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 11
- -1 siloxanes Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims 3
- 239000003960 organic solvent Substances 0.000 claims 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 21
- 238000005406 washing Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008241 heterogeneous mixture Substances 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- KTPJDYNQZVAFBU-UHFFFAOYSA-N dichloro-[chloro(dimethyl)silyl]-methylsilane Chemical compound C[Si](C)(Cl)[Si](C)(Cl)Cl KTPJDYNQZVAFBU-UHFFFAOYSA-N 0.000 description 2
- JTBAMRDUGCDKMS-UHFFFAOYSA-N dichloro-[dichloro(methyl)silyl]-methylsilane Chemical compound C[Si](Cl)(Cl)[Si](C)(Cl)Cl JTBAMRDUGCDKMS-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- SFAZXBAPWCPIER-UHFFFAOYSA-N chloro-[chloro(dimethyl)silyl]-dimethylsilane Chemical compound C[Si](C)(Cl)[Si](C)(C)Cl SFAZXBAPWCPIER-UHFFFAOYSA-N 0.000 description 1
- KQHIGRPLCKIXNJ-UHFFFAOYSA-N chloro-methyl-silylsilane Chemical class C[SiH]([SiH3])Cl KQHIGRPLCKIXNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
- C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Structural Engineering (AREA)
- Silicon Polymers (AREA)
Description
Die Erfindung betrifft die Herstellung von löslichen Methylalkoxypoly(disilyl)siloxanen aus disilanhaltigen Destillationsrückständen der Methylchlorsilansynthese oder den darin enthaltenen Disilanen. Die erhaltenen Produkte sind u. a. zur Hydrophobierung im Bauwesen verwendbar.The invention relates to the production of soluble methylalkoxypoly (disilyl) siloxanes from distillation residues containing disilane the methylchlorosilane synthesis or the disilanes contained therein. The products obtained are u. a. for waterproofing in construction usable.
Es ist hinreichend bekannt, Organochlorsilane durch Hydrolyse in Polysiloxane zu überführen. Die Verfahren arbeiten sowohl kontinuierlich als auch diskontinuierlich. Der Gehalt an SiOH- und SiCl- Gruppen in den erhaltenen Produkten ist lösemittel- und/oder verfahrensabhängig.It is well known to hydrate organochlorosilanes in Convey polysiloxanes. The procedures both work continuously as well as discontinuously. The content of SiOH and SiCl Groups in the products obtained are solvent and / or process dependent.
Für die Herstellung löslicher Methylpolysiloxane hat sich das 2- Stufen-Verfahren bewährt. In einer ersten Stufe erfolgt die Alkoxylierung der Methylchlorsilane und anschließend die Hydrolyse (DD 2 28 550, DE 8 73 433). Einstufige Verfahren haben den Nachteil der Bildung unlöslicher Produkte (US 27 58 124, DE 11 73 659). In den beschriebenen Verfahren werden als Ausgangsstoffe Monosilane eingesetzt.For the production of soluble methylpolysiloxanes, the 2- Staged procedure proven. The alkoxylation takes place in a first stage the methylchlorosilanes and then hydrolysis (DD 2 28 550, DE 8 73 433). One-step processes have the disadvantage the formation of insoluble products (US 27 58 124, DE 11 73 659). In The processes described are used as starting materials monosilanes used.
Zur Hydrolyse von Methylchlordisilanen, wie sie bei der Methylchlorsilansynthese als Hauptbestandteil der Destillationsrückstände anfallen, wurden ebenfalls Verfahren entwickelt. In US 25 75 141 wird die Hydrolyse dünner Schichten auf Trägeroberflächen beschrieben. Das noch SiCl-haltige Hydrolyseprodukt wird nicht isoliert. Gemäß FR 14 46 520 erhält man ein pulverförmiges Produkt, wobei Calciumoxid als Neutralisationsmittel Verwendung findet. Ebenfalls gelförmig sind die in EP 0 89 783, DE 30 05 743 und 35 23 543 beschriebenen Produkte. In DE 10 31 519 erhält man toluolische Lösungen von alkoxygruppenfreien Methylalkoxypoly(disilyl)siloxanen, indem man den Destillationsrückstand der Methylchlorsilanherstellung in etherischer Lösung hydrolysiert, den Ether aus der abgetrennten organischen Phase abdestilliert und das erhaltene Harz in Toluol aufnimmt. Bedingung ist, daß das Verhältnis CH₃ zu Si größer oder gleich 1 beträgt, was durch Zusatz von Dimethyldichlorsilan reguliert wird. Die Verwendung von Ether macht das Verfahren für eine technische Anwendung ungeeignet.For the hydrolysis of methylchlorodisilanes, as used in the synthesis of methylchlorosilanes as the main component of the distillation residues procedures have also been developed. In US 25 75 141 describes the hydrolysis of thin layers on carrier surfaces. The hydrolysis product still containing SiCl is not isolated. According to FR 14 46 520, a powdery product is obtained, whereby Calcium oxide is used as a neutralizing agent. Likewise are in gel form in EP 0 89 783, DE 30 05 743 and 35 23 543 described products. DE 10 31 519 gives toluene solutions of alkoxy group-free methylalkoxypoly (disilyl) siloxanes by the distillation residue of the methylchlorosilane production in hydrolyzed ethereal solution, the ether from the separated distilled organic phase and the resin obtained in toluene records. The condition is that the ratio of CH₃ to Si is greater or is equal to 1, which regulates by adding dimethyldichlorosilane becomes. The use of ether makes the process for one unsuitable for technical application.
Die bei den Methylchlorsilanen angeführte 2-Stufen-Hydrolyse wird in DE 20 23 976 dahingehend abgewandelt, daß gezielt nur 50 bis 80 Gew.-% der in der ersten Stufe erhaltenen Alkoxygruppen in Gegenwart von Zr- und Pb-Salzen hydrolysiert werden.The 2-stage hydrolysis mentioned for the methylchlorosilanes is modified in DE 20 23 976 to the effect that only 50 up to 80% by weight of the alkoxy groups obtained in the first stage Be hydrolyzed in the presence of Zr and Pb salts.
In US 46 18 666 wird für die Hydrolyse von Disilanfraktionen ein Verfahren beschrieben, bei dem zur Verhinderung von Abscheidungen (Microgele) der Zusatz von Methylchlormonosilanen, beispielsweise Dimethyldichlorsilan, beansprucht wird.In US 46 18 666 a for the hydrolysis of disilane fractions Process described in which to prevent deposition (Microgels) the addition of methylchloromonosilanes, for example Dimethyldichlorosilane is claimed.
Die Hydrolyse von unaufbereiteten Destillationsrückständen der Methylchlorsilansynthese ohne Zusatz von Methylchlormonosilanen zu löslichen Methylalkoxypoly(disilyl)siloxanen, frei von unlöslichen Produkten, in etherfreien Medien, ist mit den beschriebenen Verfahren nicht möglich.The hydrolysis of unprepared distillation residues from the Methylchlorosilane synthesis without the addition of methylchloromonosilanes soluble methylalkoxypoly (disilyl) siloxanes, free of insoluble Products, in ether-free media, are using the methods described not possible.
Ziel der Erfindung ist ein Verfahren zur Herstellung von Methylalkoxypoly(disilyl)siloxanen aus disilanhaltigen Destillationsrückständen der Methylchlorsilansynthese oder den darin enthaltenen Disilanen, die in aliphatischen oder aromatischen Kohlenwasserstoffen löslich, lufttrocknend und lagerstabil sind und deren Alkoxygehalt 1 bis 5 Gew.-% beträgt.The aim of the invention is a process for the preparation of methylalkoxypoly (disilyl) siloxanes from distillation residues containing disilane the methylchlorosilane synthesis or the contained therein Disilanes in aliphatic or aromatic hydrocarbons are soluble, air drying and storage stable and their alkoxy content Is 1 to 5 wt .-%.
Die Aufgabe der Erfindung besteht darin, ein technologisch einfaches Verfahren zur Herstellung von löslichen Methylalkoxypoly(disilyl)siloxanen aus disilanhaltigen Destillationsrückständen der Methylchlorsilansynthese oder den darin enthaltenen Disilanen zu entwickeln, welches sowohl kontinuierlich als auch diskontinuierlich durchführbar ist und auf Lösevermittler, wie z. B. Aceton, sowie auf Neutralisationsmittel verzichtet und etherfrei arbeitet.The object of the invention is a technologically simple Process for the preparation of soluble methylalkoxypoly (disilyl) siloxanes from distillation residues containing disilane Methylchlorosilane synthesis or the disilanes contained therein develop which is both continuous and discontinuous is feasible and on solvency agents such. B. acetone, as well as neutralizing agents and works ether-free.
Die Aufgabe wurde erfindungsgemäß gelöst, indem die disilanhaltigen, oberhalb 80°C siedenden Destillationsrückstände oder die darin enthaltenen Disilane mit einem Hydrolysemedium, bestehend aus konzentrierter Salzsäure und niedermolekularem aliphatischen Alkohol, in Gegenwart von Testbenzin, Petroleum, Schweröl, Hexan, Heptan, Octan, Toluol und/oder Xylol als inertem, nicht mit dem Hydrolysemedium mischbaren, Lösemitteln unter Rückfluß umgesetzt werden, wobei die dem SiCl äquimolare Menge Wasser in Form der konzentrierten Salzsäure zugesetzt wird, und die Gewichtsverhältnisse Destillationsrückstand oder Disilane zu Alkohol 1 zu 0,5 bis 1 zu 4, vorzugsweise 1 zu 2, sowie die Destillationsrückstände oder Disilane zu Lösemittel 1 zu 9 bis 1 zu 0,2, vorzugsweise 1 zu 2 bis 1 zu 0,5, betragen. Dabei wird das Lösemittel entweder dem Destillationsrückstand oder dem Hydrolysemedium zugesetzt.The object was achieved according to the invention in that the disilane-containing or distillation residues boiling above 80 ° C contained disilanes with a hydrolysis medium consisting of concentrated hydrochloric acid and low molecular weight aliphatic alcohol, in the presence of white spirit, petroleum, heavy oil, hexane, heptane, Octane, toluene and / or xylene as inert, not with the hydrolysis medium miscible solvents are reacted under reflux, where the SiCl equimolar amount of water in the form of the concentrated Hydrochloric acid is added, and the weight ratios of distillation residue or disilanes to alcohol 1 to 0.5 to 1 to 4, preferably 1 to 2, as well as the distillation residues or disilanes to solvent 1 to 9 to 1 to 0.2, preferably 1 to 2 to 1 to 0.5. The solvent becomes either the distillation residue or added to the hydrolysis medium.
Als niedermolekularer aliphatischer Alkohol wird bevorzugt Methanol oder Ethanol eingesetzt, jedoch ist auch die Verwendung von Propanol oder Butanol möglich.Methanol is preferred as the low molecular weight aliphatic alcohol or ethanol is used, but also the use of propanol or butanol possible.
Als Destillationsrückstände der Methylchlorsilansynthese werden die unaufbereiteten, oberhalb 80°C siedenden Rückstände der Methylchlorsilansynthese, die 20 bis 90 Gew.-% an Disilanen enthalten, eingesetzt. Die Disilanfraktion besteht im wesentlichen aus 1,1,2- Trichlortrimethyldisilan und 1,1,2,2-Tetrachlordimethyldisilan. Die Umsetzung von Hydrolysemedium mit Destillationsrückständen oder Disilanen erfolgt kontinuierlich oder diskontinuierlich. Die siloxanhaltige Phase ist nach Neutralwaschen mit Alkohol sofort verwendungsfähig.The distillation residues of the methylchlorosilane synthesis are the unprepared residues of methylchlorosilane synthesis boiling above 80 ° C, which contain 20 to 90% by weight of disilanes, used. The disilane fraction consists essentially of 1,1,2- Trichlorotrimethyldisilane and 1,1,2,2-tetrachlorodimethyldisilane. The implementation of hydrolysis medium with distillation residues or Disilanes take place continuously or discontinuously. The The phase containing siloxane is immediately after washing neutral with alcohol usable.
Das erfindungsgemäße Verfahren gestattet die Verwertung der Destillationsrückstände der Methylchlorsilansynthese, ohne deren vorherige Aufarbeitung, zu löslichen Methylalkoxypoly(disilyl)siloxanen, unter Vermeidung von Ether oder Zusätzen von Methylchlormonosilanen, Neutralisationsmittel oder anderen Hilfsstoffen. Die erhaltenen Produkte sind u. a. mit gutem Erfolg als Hydrophobiermittel einsetzbar.The process according to the invention permits the utilization of the distillation residues of methylchlorosilane synthesis, without the previous one Processing, to soluble methylalkoxypoly (disilyl) siloxanes, while avoiding ethers or adding methylchloromonosilanes, Neutralizing agent or other auxiliary substances. The received Products are u. a. with good success as a water repellent applicable.
Im folgenden soll das erfindungsgemäße Verfahren anhand von Beispielen dargestellt werden.In the following, the method according to the invention is intended to be based on examples being represented.
In einem mit Thermometer, Rührer, Tropftrichter und Rückflußkühler versehenen Sulfierkolben werden 1,5 kg Ethanol mit 200 g konzentrierter Salzsäure und 615 g Testbenzin gemischt und anschließend unter Rühren innerhalb von 15 Minuten 500 g unaufbereitete Destillationsrückstände der Methylchlorsilansynthese (17,1 Gew.-% Si, 41,1 Gew.-% Cl, 23 Gew.-% Disilanfraktion) zugetropft. Es wird eine Stunde unter Rückfluß gerührt.In one with a thermometer, stirrer, dropping funnel and reflux condenser provided sulfonating flask, 1.5 kg of ethanol are concentrated with 200 g Hydrochloric acid and 615 g white spirit mixed and then 500 g of unprepared distillation residues with stirring within 15 minutes methylchlorosilane synthesis (17.1% by weight Si, 41.1% by weight of Cl, 23% by weight of disilane fraction) was added dropwise. It will be one Stirred under reflux for one hour.
Das abgekühlte Gemisch bildet im Scheidetrichter sofort 2 klare Schichten. Die Siloxanschicht, 635 g, enthält nach einmaligem Waschen mit Ethanol 50 Gew.-% Siloxan, 0,05 Gew.-% Cl und 3,6 Gew.-% Ethoxygruppen. Die Lagerstabilität ist größer als 12 Monate.The cooled mixture immediately forms 2 clear ones in the separating funnel Layers. The siloxane layer, 635 g, contains after washing once with ethanol 50% by weight siloxane, 0.05% by weight Cl and 3.6% by weight Ethoxy groups. The shelf life is greater than 12 months.
120 g Destillationsrückstände (20,9 Gew.-% Si, 48,9 Gew.-% Cl, 89 Gew.-% Disilanfraktion) werden innerhalb von 30 Minuten zu einer Mischung aus 125 ml Petroleum, 50 g konzentrierter Salzsäure und 700 g Methanol gegeben. Nach 1 Stunde Rückflußkochen lassen sich 141 g Siloxanlösung (38 Gew.-% Siloxan, 0,19 Gew.-% Cl vor der Wäsche) abtrennen.120 g distillation residues (20.9% by weight Si, 48.9% by weight Cl, 89% by weight disilane fraction) become one within 30 minutes Mixture of 125 ml petroleum, 50 g concentrated hydrochloric acid and Given 700 g of methanol. After 1 hour of reflux, 141 g siloxane solution (38 wt% siloxane, 0.19 wt% Cl before washing) split off.
700 g der Methanolschicht werden nach Zugabe von 125 g Frischpetroleum erneut mit 120 g Destillationsrückständen umgesetzt und, wie oben beschrieben, verarbeitet. Es werden 162 g Siloxanlösung (40 Gew.-% Siloxan, 0,2 Gew.-% Cl vor derWäsche) erhalten.700 g of the methanol layer become after adding 125 g of fresh petroleum reacted again with 120 g of distillation residues and how described above, processed. There are 162 g of siloxane solution (40 wt% siloxane, 0.2 wt% Cl before washing).
150 g der erhaltenen Methanolschicht werden mit 550 g Frischmethanol verdünnt und 120 g Destillationsrückstände zugetropft. Man erhält 150 g Siloxanlösung (40 Gew.-% Siloxan, 0,3 Gew.-% Cl vor der Wäsche). 150 g of the methanol layer obtained are mixed with 550 g of fresh methanol diluted and 120 g of distillation residues added dropwise. You get 150 g siloxane solution (40 wt .-% siloxane, 0.3 wt .-% Cl before Laundry).
610 g Disilanfraktion (Kp.: 150 bis 160°C, bestehend aus 72 Gew.-% 1,1,2,2-Tetrachlordimethyldisilan, 24 Gew.-% 1,1,2-Trichlortrimethyldisilan sowie 4 Gew.-% 1,2-Dichlortetramethyldisilan) werden mit 590 g Testbenzin vermischt und innerhalb von 20 Minuten zu einer Mischung aus 1,5 kg Methanol und 255 g konzentrierter Salzsäure unter Rühren getropft. Es wird 1 Stunde unter Rückfluß gerührt. Nach dem Abkühlen erhält man 815 g einer klaren Siloxanschicht, die sich sofort vom Hydrolysemedium trennt und einen Siloxangehalt von 42 Gew.-% aufweist. Nach einmaligem Waschen mit 800 g Methanol beträgt der Chloridgehalt 0,01 Gew.-% und die Siloxankonzentration 51 Gew.-%.610 g disilane fraction (bp: 150 to 160 ° C, consisting of 72% by weight 1,1,2,2-tetrachlorodimethyldisilane, 24% by weight 1,1,2-trichlorotrimethyldisilane and 4% by weight of 1,2-dichlorotetramethyldisilane) mixed with 590 g white spirit and within 20 minutes to a Mixture of 1.5 kg of methanol and 255 g of concentrated hydrochloric acid added dropwise with stirring. The mixture is stirred under reflux for 1 hour. After cooling, 815 g of a clear siloxane layer are obtained separates immediately from the hydrolysis medium and has a siloxane content of 42% by weight. After washing once with 800 g of methanol the chloride content 0.01% by weight and the siloxane concentration 51 % By weight.
500 g Monomethyltrichlorsilan werden mit 500 ml Testbenzin verdünnt und in eine Mischung von 1 kg Methanol und 120 g konzentrierter Salzsäure getropft.500 g of monomethyltrichlorosilane are diluted with 500 ml white spirit and concentrated in a mixture of 1 kg of methanol and 120 g Dropped hydrochloric acid.
Nach 1 Stunde Rückflußkochen erhält man 500 g Siloxanlösung (26,8 Gew.-% Siloxan, 0,05 Gew.-% Cl vor der Wäsche) und 41 g Feststoff. Das erhaltene Siloxan war nicht lagerstabil.After refluxing for 1 hour, 500 g of siloxane solution (26.8 % By weight of siloxane, 0.05% by weight of Cl before washing) and 41 g of solid. The siloxane obtained was not stable on storage.
Die kontinuierliche Herstellung von Methylalkoxypoly(disilyl)siloxanen wird an einem Verfahrensschema (Fig. 1) erläutert.The continuous production of methylalkoxypoly (disilyl) siloxanes is explained using a process diagram ( FIG. 1).
Eine Lösung von 61 Gew.-% Destillationsrückständen in Testbenzin 1 wird in einem Reaktionskreislauf vor der Kreiselpumpe A mit 22,7 l/h dosiert. Die Kreiselpumpe erzeugt ein heterogenes Gemisch 2 aus Destillationsrückstandslösung und einem Hydrolysemedium 3, bestehend aus 47 Gew.-% Hydrolysemedim 6, 48,8 Gew.-% Methanol 9 aus der Wascheinheit F sowie 4,2 Gew.-% Wasser, und gewährleistet einen Kreislauf des heterogenen Gemisches 2. Das Gefäß B hat einen heizbaren Mantel (T=60°C) und dient der Volumenvergrößerung des Reaktionskreislaufes. Das Hydrolysemedim 3 wird mit 47,6 l/h dosiert. Die Abnahme des bei der Reaktion entstehenden gasförmigen Chlorwasserstoffes 4 erfolgt über den Rückflußkühler C, die Entnahme des Reaktionsgemisches 5 wird dem Trenngefäß D zugeleitet, an dessen Boden verbrauchtes Hydrolysemedium 6 abgenommen und zum Teil dem Reaktionskreislauf zugeführt wird. Dem restlichen Hydrolysemedium 6 wird durch Destillation das Methanol entzogen, entstehendes Methylchlorid sowie gasförmiger Chlorwasserstoff werden gewonnen. Die am Kopf der Trennstufe D abgenommene Rohsiloxanlösung 7 wird im mit Füllkörpern versehenen Kolonnenteil E der Wascheinheit F im Gegenstrom mit Methanol 8 (Volumenverhältnis Methanol zu zulaufendem Rohsiloxan 1 zu 1) gewaschen. Das über Kopf abgehende Waschmethanol 9 wird mit Wasser 10 versetzt und vollständig, gemeinsam mit dem einen Teil des verbrauchten Hydrolysemediums 6, dem Reaktionskreislauf zugeführt. Die am Boden der Wascheinheit F abgenommene Siloxanlösung 11 ist klar und hat eine Konzentration von 52 Gew.-% Siloxan, der Methoxygehalt beträgt 4,9 Gew.-%, die Lagerstabilität ist größer als 12 Monate, der Cl-Gehalt beträgt 0,003 Gew.-%.A solution of 61% by weight of distillation residues in white spirit 1 is metered in a reaction circuit upstream of centrifugal pump A at 22.7 l / h. The centrifugal pump produces a heterogeneous mixture 2 of distillation residue solution and a hydrolysis medium 3 , consisting of 47% by weight hydrolysis medium 6 , 48.8% by weight methanol 9 from the washing unit F and 4.2% by weight water, and ensures one Circulation of the heterogeneous mixture 2 . The vessel B has a heatable jacket (T = 60 ° C) and serves to increase the volume of the reaction circuit. The hydrolysis medium 3 is metered in at 47.6 l / h. The gaseous hydrogen chloride 4 formed in the reaction is removed via the reflux condenser C, and the reaction mixture 5 is removed to the separation vessel D, at the bottom of which the used hydrolysis medium 6 is removed and partly fed to the reaction circuit. The remaining hydrolysis medium 6 is removed from the methanol by distillation, resulting methyl chloride and gaseous hydrogen chloride are obtained. The crude siloxane solution 7 taken off at the top of the separation stage D is washed in the column part E of the washing unit F provided with packing in countercurrent with methanol 8 (volume ratio of methanol to the crude siloxane to be fed in 1: 1). The washing methanol 9 leaving overhead is mixed with water 10 and completely, together with part of the used hydrolysis medium 6 , fed to the reaction cycle. The siloxane solution 11 taken off at the bottom of the washing unit F is clear and has a concentration of 52% by weight of siloxane, the methoxy content is 4.9% by weight, the storage stability is greater than 12 months, the Cl content is 0.003% by weight. -%.
Im folgenden soll die hervorragende Wirkung der erfindungsgemäß
hergestellten Methylalkoxypoly(disilyl)siloxane als Hydrophobiermittel
demonstriert werden:
Als Hydrophobierlösung werden nach einem der vorher beschriebenen
Verfahren kontinuierlich oder diskontinuierlich hergestellte
Methylalkoxypoly(disilyl)siloxane als Lösung von 7 Gew.-Teilen von
Wirkstoff in 93 Gew.-Teilen Benzin verwendet.The outstanding effect of the methylalkoxypoly (disilyl) siloxanes prepared according to the invention as water repellents is to be demonstrated below:
As a water repellent solution, methylalkoxypoly (disilyl) siloxanes prepared continuously or batchwise as a solution of 7 parts by weight of active ingredient in 93 parts by weight of gasoline are used according to one of the processes described above.
Probekörper der Mörtelgruppe 2 (entsprechend einem Mischungsverhältnis Zement zu Kalk zu Normsand wie 1 zu 3 zu 8) in den Abmessungen 100 mm × 70 mm × 20 mm wurden nach der Herstellung 2 Wochen bei Raumtemperatur getrocknet und anschließend 10 Sekunden in die oben beschriebene Hydrophobierlösung getaucht. Nach der Behandlung wurden die Probekörper erneut 2 Wochen bei Raumtemperatur getrocknet, anschließend zur Prüfung des Hydrophobiereffektes einer Wasserlagerung (2 cm überdeckend) ausgesetzt und die prozentuale Wasseraufnahme nach jeweils 2, 6, 24 und 48 Stunden bestimmt. Zum Vergleich gegenüber dem erfindungsgemäßen Produkt dient ein übliches Hydrophobiermittel auf Siliconbasis mit einem Harzanteil von 7 Gew.-%.Test specimens of mortar group 2 (corresponding to a mixing ratio of cement to lime to standard sand such as 1 to 3 to 8) in the dimensions 100 mm × 70 mm × 20 mm were dried after production for 2 weeks at room temperature and then immersed in the hydrophobicizing solution described above for 10 seconds . After the treatment, the test specimens were dried again at room temperature for 2 weeks, then exposed to water storage (covering 2 cm) to test the hydrophobing effect and the percentage water absorption was determined after 2, 6, 24 and 48 hours. A conventional silicone-based water repellent with a resin content of 7% by weight is used for comparison with the product according to the invention.
Aufstellung der verwendeten BezugszeichenList of the reference numerals used
1 Destillationsrückstandslösung
2 heterogenes Gemisch
3 Hydrolysemedium
4 Chlorwasserstoff
5 Reaktionsgemisch
6 verbrauchtes Hydrolysemedium
7 Rohsiloxanlösung
8 Methanol
9 Waschmethanol
10 Wasser
11 Siloxanlösung
A Kreiselpumpe
B Gefäß
C Rückflußkühler
D Trenngefäß
E Kolonnenteil
F Wascheinheit 1 distillation residue solution
2 heterogeneous mixture
3 hydrolysis medium
4 hydrogen chloride
5 reaction mixture
6 used hydrolysis medium
7 crude siloxane solution
8 methanol
9 washing methanol
10 water
11 siloxane solution
A centrifugal pump
B vessel
C reflux condenser
D separation vessel
E column section
F washing unit
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904033157 DE4033157A1 (en) | 1990-10-12 | 1990-10-12 | Soluble methyl:alkoxy-poly-di:silyl-siloxane single step prodn. - from di:silane contg. residue by refluxing with alcoholic hydrochloric acid in presence of inert solvent, useful as waterproofing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904033157 DE4033157A1 (en) | 1990-10-12 | 1990-10-12 | Soluble methyl:alkoxy-poly-di:silyl-siloxane single step prodn. - from di:silane contg. residue by refluxing with alcoholic hydrochloric acid in presence of inert solvent, useful as waterproofing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE4033157A1 DE4033157A1 (en) | 1992-04-16 |
| DE4033157C2 true DE4033157C2 (en) | 1993-09-09 |
Family
ID=6416584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19904033157 Granted DE4033157A1 (en) | 1990-10-12 | 1990-10-12 | Soluble methyl:alkoxy-poly-di:silyl-siloxane single step prodn. - from di:silane contg. residue by refluxing with alcoholic hydrochloric acid in presence of inert solvent, useful as waterproofing agent |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4033157A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8084097B2 (en) | 2006-02-20 | 2011-12-27 | Dow Corning Corporation | Silicone resin film, method of preparing same, and nanomaterial-filled silicone composition |
| US8084532B2 (en) | 2006-01-19 | 2011-12-27 | Dow Corning Corporation | Silicone resin film, method of preparing same, and nanomaterial-filled silicone composition |
| US8088449B2 (en) | 2005-02-16 | 2012-01-03 | Dow Corning Toray Co., Ltd. | Reinforced silicone resin film and method of preparing same |
| US8092910B2 (en) | 2005-02-16 | 2012-01-10 | Dow Corning Toray Co., Ltd. | Reinforced silicone resin film and method of preparing same |
| US8273448B2 (en) | 2007-02-22 | 2012-09-25 | Dow Corning Corporation | Reinforced silicone resin films |
| US8283025B2 (en) | 2007-02-22 | 2012-10-09 | Dow Corning Corporation | Reinforced silicone resin films |
| US8334022B2 (en) | 2005-08-04 | 2012-12-18 | Dow Corning Corporation | Reinforced silicone resin film and method of preparing same |
| US8912268B2 (en) | 2005-12-21 | 2014-12-16 | Dow Corning Corporation | Silicone resin film, method of preparing same, and nanomaterial-filled silicone composition |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2744727A1 (en) * | 1996-02-14 | 1997-08-14 | Rhone Poulenc Chimie | Water soluble solid poly:siliconates |
| JP2010512453A (en) | 2006-07-27 | 2010-04-22 | ダウ・コーニング・コーポレイション | Method for producing silicone resin |
| ES2727007T3 (en) * | 2006-07-27 | 2019-10-11 | Dow Silicones Corp | Silicone resins, silicone composition, and coated substrates |
| KR20090107529A (en) * | 2007-02-06 | 2009-10-13 | 다우 코닝 코포레이션 | Silicone resin, silicone composition, coated substrate, and reinforced silicone resin film |
| EP2142589A2 (en) * | 2007-05-01 | 2010-01-13 | Dow Corning Corporation | Reinforced silicone resin film |
| WO2008134241A1 (en) * | 2007-05-01 | 2008-11-06 | Dow Corining Corporation | Nanomaterial-filled silicone composition and reinforced silicone resin film |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2575141A (en) * | 1948-10-26 | 1951-11-13 | Gen Electric | Surfaces having low adhesion to ice |
| DE873433C (en) * | 1949-05-26 | 1953-04-13 | Rudolf Decker | Process for the production of silicone varnishes |
| US2758124A (en) * | 1952-04-11 | 1956-08-07 | Gen Electric | Continuous hydrolysis of organohalogenosilanes |
| FR1081726A (en) * | 1952-08-18 | 1954-12-22 | Rhone Poulenc Sa | New organosilicon resins and their preparations |
| DE1173659B (en) * | 1957-10-31 | 1964-07-09 | Bayer Ag | Process for the production of uniformly finely divided solid hydrolysis products from liquid silane derivatives |
| FR1446520A (en) * | 1964-07-17 | 1966-07-22 | Midland Silicones Ltd | Organosilicon composition which can be used in particular in building materials |
| US4221691A (en) * | 1979-02-16 | 1980-09-09 | Dow Corning Corporation | Method of hydrolyzing chlorosilanes |
| US4408030A (en) * | 1982-03-22 | 1983-10-04 | Dow Corning Corporation | Waste chlorosilane treatment |
| FR2564470B1 (en) * | 1984-05-18 | 1987-01-02 | Rhone Poulenc Spec Chim | ORGANOSILIC RESIN WITH DISILANIC PATTERNS AND IMPROVED THERMOMECHANICAL PROPERTIES AND IN ADDITION FOR USE IN WATERPROOFING OF THE BUILDING |
| DD228550A1 (en) * | 1984-11-13 | 1985-10-16 | Nuenchritz Chemie | METHOD FOR CONTINUOUS PRODUCTION OF METHYL SILICONE RESINS |
| DE3523543A1 (en) * | 1985-07-02 | 1987-01-15 | Bayer Ag | METHOD FOR THE PROCESSING OF HYDROLYSIS RESIDUES FROM THE METHYLCHLORSILAN SYNTHESIS |
-
1990
- 1990-10-12 DE DE19904033157 patent/DE4033157A1/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8088449B2 (en) | 2005-02-16 | 2012-01-03 | Dow Corning Toray Co., Ltd. | Reinforced silicone resin film and method of preparing same |
| US8092910B2 (en) | 2005-02-16 | 2012-01-10 | Dow Corning Toray Co., Ltd. | Reinforced silicone resin film and method of preparing same |
| US8334022B2 (en) | 2005-08-04 | 2012-12-18 | Dow Corning Corporation | Reinforced silicone resin film and method of preparing same |
| US8912268B2 (en) | 2005-12-21 | 2014-12-16 | Dow Corning Corporation | Silicone resin film, method of preparing same, and nanomaterial-filled silicone composition |
| US8084532B2 (en) | 2006-01-19 | 2011-12-27 | Dow Corning Corporation | Silicone resin film, method of preparing same, and nanomaterial-filled silicone composition |
| US8084097B2 (en) | 2006-02-20 | 2011-12-27 | Dow Corning Corporation | Silicone resin film, method of preparing same, and nanomaterial-filled silicone composition |
| US8273448B2 (en) | 2007-02-22 | 2012-09-25 | Dow Corning Corporation | Reinforced silicone resin films |
| US8283025B2 (en) | 2007-02-22 | 2012-10-09 | Dow Corning Corporation | Reinforced silicone resin films |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4033157A1 (en) | 1992-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE4033157C2 (en) | ||
| EP0242798A2 (en) | Aqueous siloxane emulsions and their use | |
| EP0002745A1 (en) | Curable organopolysiloxane compositions containing titanium esters | |
| DE2642811C3 (en) | Oxysilanol compounds, process for their preparation and their use | |
| EP0170287A1 (en) | Process for stabilizing organosiloxanes | |
| DE3546376A1 (en) | BIS (AMINOALKYL) DISILOXANES AND METHOD FOR THE PRODUCTION THEREOF | |
| DE1495868C3 (en) | Process for the preparation of organopolysiloxanes containing acyloxyalkyl groups | |
| EP0514737A1 (en) | Method for making organopolysiloxanes with at least one Si-bound cyclopentadienyl-group | |
| DE3606262A1 (en) | SILYLCARBAMATE AND METHOD FOR THE PRODUCTION THEREOF | |
| EP0115772B1 (en) | Process for the splitting of organosiloxanes and resulting products and their applications | |
| DE69828796T2 (en) | HIGHLY BRANCHED ALKYLSILSESQUIOXANEFLUIDS | |
| DE2330887A1 (en) | USE OF ALKYL / ARYL-ALCOXY POLYSILOXANES FOR IMPRAEGNATION | |
| DE1241827B (en) | Process for the preparation of tertiary halobutoxysilanes | |
| DE1645651A1 (en) | Process for the preparation of polysilarylene siloxanes | |
| DE1595239B2 (en) | PROCESS FOR PRODUCING LINEAR ORGANOPOLYSILOXANES | |
| DE1125180B (en) | Process for the hydrolysis of chlorosilanes with hydrogen or organofunctional groups directly bonded to silicon | |
| DE1420470A1 (en) | Process for the preparation of carbalkoxyalkyl-containing organopolysiloxanes | |
| DE2738303C3 (en) | Process for the preparation of chlorine-containing siloxanes and such compounds | |
| DE959909C (en) | Process for the preparation of alkyl or aryl silanes or -siloxanes | |
| DE1099743B (en) | Process for the preparation of stannosiloxanes | |
| DE1568712A1 (en) | Acyloxysiloxanes and processes for their preparation | |
| DE1039516B (en) | Process for the preparation of acyloxysilicon compounds | |
| DE4033156A1 (en) | Prepn. of methyl:alkoxy:oligo(di:silyl)-siloxane cpds. - by two stage alkoxylation of distn. residue from methyl:chlorosilane synthesis or di:silane(s) from residue | |
| DE862607C (en) | Process for the preparation of triorganosilylphenoxysilanes | |
| DE1214876B (en) | Diorganopolysiloxane molding compounds that are stable in the diluted state |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OP8 | Request for examination as to paragraph 44 patent law | ||
| D2 | Grant after examination | ||
| 8364 | No opposition during term of opposition | ||
| 8339 | Ceased/non-payment of the annual fee |